Free-radical polymerization of bicyclobutanes

Swartz, Thomas D.; Hall, H. K.

doi:10.1021/ja00730a024

Cited by 21 publications

(6 citation statements)

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“…Physical data: bp 96-105 °C (43 mmHg). The NMR and IR spectra were identical to the spectra reported by Hall et al4 13C NMR (CDCls), 5 (ppm): 174.55 (0=0), 51.44 (C3 cis), 50.72 (C3 trans), 47.42 (CH3 cis),37.31 (C2,4 cis), 36.70 (C2>4 trans), 33.73 (Ci cis), 32.13 (Ci trans). Mass spectrum, m/e: 148 (2), 117 (22), 113 (95), 55 (102).…”

Section: Methodssupporting

confidence: 70%

Synthesis and polymerization of alkyl 1-bicyclobutanecarboxylates

Drujon¹,

Riess²,

Hall³

et al. 1993

Macromolecules

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Bicyclobutane monomers substituted with an ester group at the 1 position were synthesized using a practical synthesis route, starting from 1,1 -cyclobutanedicarboxylic acid, which is adaptable to the synthesis of various bicyclobutane esters and can be scaled up. Four new bicyclobutane monomers were prepared using this method, namely ethyl, isopropyl, ß,ß,ß-trifluoroethyl, and phenyl 1-bicyclobutanecarboxylate. These bicyclobutanecarboxylates were subjected to free radical polymerization under various conditions. The bicyclobutane monomers behave very similarly to their vinyl counterparts. Chain transfer to polymer occurs to some extent, especially when the size of the substituent is relatively small (methyl ester). Excessively high molecular weights and gelation can be controlled by addition of a chain-transfer agent. The temperature, the size of the ester group, or the nature of the initiator has no marked influence on the stereochemistry of the bicyclobutane polymer backbones. Poly(methyI 1-bicyclobutanecarboxylate) is an optically clear material with a refractive index no25 = 1.52. Its resistance to thermal degradation is excellent. Polymers from this family exhibited surprisingly low Tg's, which probably result from an unexpectedly high flexibility of the bicyclobutane polymer backbone, as shown by molecular modeling.

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Section: Methodssupporting

confidence: 70%

Synthesis and polymerization of alkyl 1-bicyclobutanecarboxylates

Drujon¹,

Riess²,

Hall³

et al. 1993

Macromolecules

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“… The free‐radical copolymerization of the electrophilic bicyclobutanes with vinyl monomers occurred readily. The reactivity radios were determined, and they followed the same pattern as would be expected for vinyl monomers 9. Recently, we have successfully carried out atom transfer radical polymerization (ATRP) on methyl bicyclobutane‐1‐carboxylate,10, 11 confirming the radical nature of these polymerizations.…”

Section: Bicyclobutanessupporting

confidence: 53%

Bicyclobutanes and cyclobutenes: Unusual carbocyclic monomers

Hall

Padías

2003

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Bicyclobutanes and cyclobutenes substituted with electron-attracting groups represent novel classes of reactive monomers. They readily undergo free-radical and anionic polymerizations to give high polymers consisting of 1,3-and 1,2-enchained cyclobutane rings, respectively.They also copolymerize readily with conventional vinyl monomers. These polymers display numerous attractive properties in comparison with their vinyl counterparts, including enhanced thermal stability, superior optical properties, and higher glass-transition temperatures. The syntheses of these monomers are reviewed, and suggestions toward future larger scale production are made.

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“…In order to place these copolymerization results on a more quantitative basis, determinations of monomer reactivity ratios were carried out (Swartz and Hall, 1971). Conventional reactivity plots were satisfactorily linear, and the results are given in Table IX.…”

Section: Radica Imentioning

confidence: 99%